CN107082447A - A kind of preparation method of the hollow Cerium titanate microballoon of macropore - Google Patents
A kind of preparation method of the hollow Cerium titanate microballoon of macropore Download PDFInfo
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- CN107082447A CN107082447A CN201710286590.2A CN201710286590A CN107082447A CN 107082447 A CN107082447 A CN 107082447A CN 201710286590 A CN201710286590 A CN 201710286590A CN 107082447 A CN107082447 A CN 107082447A
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- macropore
- electric heating
- autoclave
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- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 35
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 35
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 58
- 239000012065 filter cake Substances 0.000 claims abstract description 36
- 239000002253 acid Substances 0.000 claims abstract description 31
- 239000012695 Ce precursor Substances 0.000 claims abstract description 18
- 239000000047 product Substances 0.000 claims abstract description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 8
- 239000008103 glucose Substances 0.000 claims abstract description 8
- -1 isopropyl alcohol ester Chemical class 0.000 claims abstract description 8
- 239000003381 stabilizer Substances 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract 3
- 238000005485 electric heating Methods 0.000 claims description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 238000003760 magnetic stirring Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 15
- 238000004821 distillation Methods 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 14
- 239000004744 fabric Substances 0.000 claims description 14
- 239000004570 mortar (masonry) Substances 0.000 claims description 14
- 229910052573 porcelain Inorganic materials 0.000 claims description 14
- 230000001105 regulatory effect Effects 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 229910001220 stainless steel Inorganic materials 0.000 claims description 14
- 239000010935 stainless steel Substances 0.000 claims description 14
- 238000000967 suction filtration Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 150000002823 nitrates Chemical class 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- 230000005619 thermoelectricity Effects 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 2
- 238000011001 backwashing Methods 0.000 claims 2
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- 239000002826 coolant Substances 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 abstract 2
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 abstract 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 abstract 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 abstract 1
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 238000009413 insulation Methods 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 238000000746 purification Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000011796 hollow space material Substances 0.000 description 3
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 3
- HRHBQGBPZWNGHV-UHFFFAOYSA-N azane;bromomethane Chemical compound N.BrC HRHBQGBPZWNGHV-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/12—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of actinides
-
- B01J35/39—
-
- B01J35/651—
-
- B01J35/653—
-
- B01J35/657—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
Abstract
A kind of preparation method of the hollow Cerium titanate microballoon of macropore, prepares template presoma：Prepared with n-butanol, glucose solution, PEG 20000, DTAB and stabilizer SY 5；Hydrothermal Synthesiss macropore template：Template presoma is incubated 36 h at 180 ~ 200 DEG C, sonicated, filtering, drying are made；Metatitanic acid cerium precursor：Including metatitanic acid isopropyl alcohol ester, absolute ethyl alcohol, acetone, directed agents AP 3, cerous nitrate；Hydrothermal Synthesiss Cerium titanate：Metatitanic acid cerium precursor is incubated 72 h at 220 ~ 240 DEG C, then through being cleaned by ultrasonic, filtering and drying process；Heat treatment：Filter cake is calcined into 3 ~ 6 h at 1200 ~ 1350 DEG C, grinding is produced.Preparation process condition has operability, and product particle size is uniform, shape is complete, and product photocatalytic activity is high and stably.
Description
Technical field
The invention belongs to environmental purification function Material Field, and in particular to a kind of preparation side of the hollow Cerium titanate microballoon of macropore
Method.
Background technology
Large pore material（Macroporous materials）Aperture is more than 50 nm.Pore structure in large pore material can be into
Enter the passage of pore passage structure for adsorption molecule.Large pore material has that specific surface area is larger, density is low, low-refraction and heat
The features such as coefficient of expansion is relatively low so that macropore hollow material is widely used in catalyst carrier, radioresistance skin-material, chargeable
Battery etc..Macropore hollow material has unique excellent photocatalysis property, increased specific surface area is not only due to, while hollow
Structure can stablize its activated centre.In hollow shell structure particles, its internal pore passage structure gap provides a large amount of suitable
Space is used for catalytic reaction.
Cerium titanate is a kind of titanate material with particular advantages, by the extensive concern of all circles, it is considered to be a kind of
The environmental pollution purification type catalysis material of great development prospect.Although powder Cerium titanate has higher purification activity, urge
The recycling of agent turns into people's issues that need special attention in practical application.Nano-powder Cerium titanate photochemical catalyst is used to disappear
During except water pollutant, there is catalyst recovery difficulty, catalyst and easily inactivate, need to maintain catalyst by power stirring
Suspension the shortcomings of.Novel nano structure catalyst such as nanometer macropore tiny balloon etc. has low-density, the characteristic of high-ratio surface,
Catalyst can be made to be easy to separate from solution according to the difference of catalyst use condition simultaneously.Macropore hollow material is used as one kind
New environmental purification function material has broad application prospects.This patent discloses a kind of system of the hollow Cerium titanate microballoon of macropore
Preparation Method.
The content of the invention
The problem of existing for prior art, the present invention is intended to provide a kind of preparation side of the hollow Cerium titanate microballoon of macropore
Method.
The technical solution adopted by the present invention is：
A kind of preparation method of the hollow Cerium titanate microballoon of macropore, including following processing steps：
1st, template presoma is prepared
By 30 ~ 40 mL n-butanols, the 3 mol/L mL of glucose solution 18 ~ 25,5.6 ~ 7.5 g PEG 20000s, 1.5 ~
2.7 mL DTABs and 0.5 ~ 1.2 g stabilizers SY-5 are added in 100 mL twoport round-bottomed flasks；
Flask is placed in precise temperature control electric heating bag, in flask center, interface installs spherical condensation tube, is situated between by cooling of running water
Matter, thermometric thermoelectricity corner is installed in another interface of flask.By adjust electric heating bag heating-up temperature using control in flask solution temperature as
60 DEG C, the min of time 50 is maintained the reflux in this temperature, room temperature is subsequently cooled to, it is standby.
2nd, Hydrothermal Synthesiss macropore template
The template presoma of preparation is moved into volume in the 100 mL cup-like liner being made up of polytetrafluoroethylmaterial material, to cover
Lid, is placed in stainless steel autoclave；
Autoclave is put in constant temperature electric heating drying box, constant temperature electric heating drying box temperature is risen into 180 ~ 200 DEG C, insulation
36 h；In the process, pressure no more than 3MPa in autoclave is controlled by regulating thermostatic electrically heated drying cabinet temperature；
After device is cooled to room temperature, product is transferred in 200 mL beakers, with 45 MHz frequencies in ultrasonic cleaner
Ultrasonically treated 20 minutes；
By gained solidliquid mixture by cloth funnel suction filtration, after distillation water washing 3 times, then with absolute ethyl alcohol cyclic washing 3
It is secondary, obtain solid filter cake；
Filter cake is placed in constant temperature electric heating drying box, 6 h are dried at 90 DEG C, are then clayed into power in agate mortar, it is standby
With.
3rd, prepared by metatitanic acid cerium precursor
5.2 ~ 6.3 mL metatitanic acid isopropyls alcohol esters, 30 ~ 35 mL absolute ethyl alcohols, 12 ~ 14 mL are separately added into 100 mL beakers
Acetone and 1.2 ~ 1.3 g directed agents AP-3,20 min are stirred on magnetic stirring apparatus, A liquid is used as；
30 mL absolute ethyl alcohols, 3.6 g Surfactant OPs -3,500 mg macropores templates, 50 ~ 60 are added in 200 mL beakers
ML distilled water and 1.5 ~ 2.1 g cerous nitrates, 20 min are stirred on magnetic stirring apparatus, B liquid is used as；
A drops are added in B liquid during magnetic agitation and continue to stir 30 min, by mixed liquor in ultrasonic cleaner
It is standby with ultrasonically treated 1 h of 45 MHz frequencies.
4th, Hydrothermal Synthesiss Cerium titanate
Metatitanic acid cerium precursor is moved into volume in the 200 mL cup-like liner being made up of polytetrafluoroethylmaterial material, to close the lid
Son, is placed in stainless steel autoclave；
Autoclave is put in constant temperature electric heating drying box, constant temperature electric heating drying box temperature is risen into 220 ~ 240 DEG C, insulation
72 h.In the process, pressure no more than 3MPa in autoclave is controlled by regulating thermostatic electrically heated drying cabinet temperature；
After device is cooled to room temperature, product is transferred in 200 mL beakers, with 45 MHz frequencies in ultrasonic cleaner
Ultrasonically treated 20 minutes；
By gained solidliquid mixture by cloth funnel suction filtration, after distillation water washing 3 times, then with absolute ethyl alcohol cyclic washing 3
It is secondary, obtain solid filter cake；
Filter cake is placed in constant temperature electric heating drying box, 6 h are dried at 120 DEG C, it is standby.
5th, it is heat-treated
Filter cake is put into porcelain crucible and is placed in program control cabinet-type electric furnace, furnace temperature is risen to 10 DEG C/min heating rates
1200 ~ 1350 DEG C, in this temperature calcination 3 ~ 6 h.Taken out after electric furnace is cooled to room temperature, ground in porcelain mortar and macropore is made
Hollow Cerium titanate microballoon.
Compared with prior art, the advantage of the invention is that：
1st, the invention provides a kind of method for preparing the hollow Cerium titanate microballoon of new macroporous, the key technology of this method is to system
The reasonably optimizing of standby technique and composition of raw materials；
2nd, the present invention reasonably have selected macropore template and solvent and key component in metatitanic acid cerium precursor solution, to preparing work
The need for the selection of skill procedure parameter also fully takes into account the stability and activity of prepared material；
3rd, the preparation process condition that the present invention is provided has operability, and product particle size is uniform, shape is complete, and product light is urged
Change activity high and stably.
Embodiment
Embodiment 1
A kind of preparation method of the hollow Cerium titanate microballoon of macropore, including following processing steps：
Step 1：Prepare template presoma
By 32 mL n-butanols, the 3 mol/L mL of glucose solution 18,5.6 g PEG 20000s, 1.6 mL dodecyls
Trimethylammonium bromide and 0.7 g stabilizers SY-5 are added in 100 mL twoport round-bottomed flasks；
Flask is placed in precise temperature control electric heating bag, in flask center, interface installs spherical condensation tube, is situated between by cooling of running water
Matter, thermometric thermoelectricity corner is installed in another interface of flask；By adjust electric heating bag heating-up temperature using control in flask solution temperature as
60 DEG C, the min of time 50 is maintained the reflux in this temperature, room temperature is subsequently cooled to, it is standby.
Step 2：Hydrothermal Synthesiss macropore template
The template presoma of preparation is moved into volume in the 100 mL cup-like liner being made up of polytetrafluoroethylmaterial material, to cover
Lid, is placed in stainless steel autoclave；
Autoclave is put in constant temperature electric heating drying box, constant temperature electric heating drying box temperature is risen into 180 ~ 200 DEG C, insulation
36 h.In the process, pressure no more than 3MPa in autoclave is controlled by regulating thermostatic electrically heated drying cabinet temperature；
After device is cooled to room temperature, product is transferred in 200 mL beakers, with 45 MHz frequencies in ultrasonic cleaner
Ultrasonically treated 20 minutes；
By gained solidliquid mixture by cloth funnel suction filtration, after distillation water washing 3 times, then with absolute ethyl alcohol cyclic washing 3
It is secondary, obtain solid filter cake；
Filter cake is placed in constant temperature electric heating drying box, 6 h are dried at 90 DEG C, are then clayed into power in agate mortar, it is standby
With.
Step 3：It is prepared by metatitanic acid cerium precursor
5.3 mL metatitanic acid isopropyls alcohol esters, 30 mL absolute ethyl alcohols, 12 mL acetone and 1.2 g are separately added into 100 mL beakers
Directed agents AP-3, stirs 20 min on magnetic stirring apparatus, is used as A liquid；
30 mL absolute ethyl alcohols, 3.6 g Surfactant OPs -3,500 mg macropores templates, 50 mL are added in 200 mL beakers
Distilled water and 1.5 g cerous nitrates, 20 min are stirred on magnetic stirring apparatus, B liquid is used as；
A drops are added in B liquid during magnetic agitation and continue to stir 30 min, by mixed liquor in ultrasonic cleaner
It is standby with ultrasonically treated 1 h of 45 MHz frequencies.
Step 4：Hydrothermal Synthesiss Cerium titanate
Metatitanic acid cerium precursor is moved into volume in the 200 mL cup-like liner being made up of polytetrafluoroethylmaterial material, to close the lid
Son, is placed in stainless steel autoclave；
Autoclave is put in constant temperature electric heating drying box, constant temperature electric heating drying box temperature is risen into 220 ~ 240 DEG C, insulation
72 h.In the process, pressure no more than 3MPa in autoclave is controlled by regulating thermostatic electrically heated drying cabinet temperature；
After device is cooled to room temperature, product is transferred in 200 mL beakers, with 45 MHz frequencies in ultrasonic cleaner
Ultrasonically treated 20 minutes；
By gained solidliquid mixture by cloth funnel suction filtration, after distillation water washing 3 times, then with absolute ethyl alcohol cyclic washing 3
It is secondary, obtain solid filter cake；
Filter cake is placed in constant temperature electric heating drying box, 6 h are dried at 120 DEG C, it is standby.
Step 5：Heat treatment
Filter cake is put into porcelain crucible and is placed in program control cabinet-type electric furnace, furnace temperature is risen to 10 DEG C/min heating rates
1200 DEG C, in this temperature calcination 5 h.Taken out after electric furnace is cooled to room temperature, ground in porcelain mortar and the hollow metatitanic acid of macropore is made
Cerium microballoon.
The rotating speed for the magnetic stirring apparatus being related in the present embodiment is 200 r/min.
Embodiment 2
A kind of preparation method of the hollow Cerium titanate microballoon of macropore, including following processing steps：
Step 1：Prepare template presoma
By 35 mL n-butanols, the 3 mol/L mL of glucose solution 21,6 g PEG 20000s, 1.9 mL dodecyls three
Methyl bromide ammonium and 0.7 g stabilizers SY-5 are added in 100 mL twoport round-bottomed flasks；
Flask is placed in precise temperature control electric heating bag, in flask center, interface installs spherical condensation tube, is situated between by cooling of running water
Matter, thermometric thermoelectricity corner is installed in another interface of flask.By adjust electric heating bag heating-up temperature using control in flask solution temperature as
60 DEG C, the min of time 50 is maintained the reflux in this temperature, room temperature is subsequently cooled to, it is standby.
Step 2：Hydrothermal Synthesiss macropore template
The template presoma of preparation is moved into volume in the 100 mL cup-like liner being made up of polytetrafluoroethylmaterial material, to cover
Lid, is placed in stainless steel autoclave；
Autoclave is put in constant temperature electric heating drying box, constant temperature electric heating drying box temperature is risen into 180 ~ 200 DEG C, insulation
36 h.In the process, pressure no more than 3MPa in autoclave is controlled by regulating thermostatic electrically heated drying cabinet temperature；
After device is cooled to room temperature, product is transferred in 200 mL beakers, with 45 MHz frequencies in ultrasonic cleaner
Ultrasonically treated 20 minutes；
By gained solidliquid mixture by cloth funnel suction filtration, after distillation water washing 3 times, then with absolute ethyl alcohol cyclic washing 3
It is secondary, obtain solid filter cake；
Filter cake is placed in constant temperature electric heating drying box, 6 h are dried at 90 DEG C, are then clayed into power in agate mortar, it is standby
With.
Step 3：It is prepared by metatitanic acid cerium precursor
5.8 mL metatitanic acid isopropyls alcohol esters, 32 mL absolute ethyl alcohols, 12 mL acetone and 1.2 g are separately added into 100 mL beakers
Directed agents AP-3, stirs 20 min on magnetic stirring apparatus, is used as A liquid；
30 mL absolute ethyl alcohols, 3.6 g Surfactant OPs -3,500 mg macropores templates, 55 mL are added in 200 mL beakers
Distilled water and 1.8 g cerous nitrates, 20 min are stirred on magnetic stirring apparatus, B liquid is used as；
A drops are added in B liquid during magnetic agitation and continue to stir 30 min, by mixed liquor in ultrasonic cleaner
It is standby with ultrasonically treated 1 h of 45 MHz frequencies.
Step 4：Hydrothermal Synthesiss Cerium titanate
Metatitanic acid cerium precursor is moved into volume in the 200 mL cup-like liner being made up of polytetrafluoroethylmaterial material, to close the lid
Son, is placed in stainless steel autoclave；
Autoclave is put in constant temperature electric heating drying box, constant temperature electric heating drying box temperature is risen into 220 ~ 240 DEG C, insulation
72 h.In the process, pressure no more than 3MPa in autoclave is controlled by regulating thermostatic electrically heated drying cabinet temperature；
After device is cooled to room temperature, product is transferred in 200 mL beakers, with 45 MHz frequencies in ultrasonic cleaner
Ultrasonically treated 20 minutes；
By gained solidliquid mixture by cloth funnel suction filtration, after distillation water washing 3 times, then with absolute ethyl alcohol cyclic washing 3
It is secondary, obtain solid filter cake；
Filter cake is placed in constant temperature electric heating drying box, 6 h are dried at 120 DEG C, it is standby.
Step 5：Heat treatment
Filter cake is put into porcelain crucible and is placed in program control cabinet-type electric furnace, furnace temperature is risen to 10 DEG C/min heating rates
1260 DEG C, in this temperature calcination 5 h.Taken out after electric furnace is cooled to room temperature, ground in porcelain mortar and the hollow metatitanic acid of macropore is made
Cerium microballoon.
The rotating speed for the magnetic stirring apparatus being related in the present embodiment is 200 r/min.
Embodiment 3
A kind of preparation method of the hollow Cerium titanate microballoon of macropore, including following processing steps：
Step 1：Prepare template presoma
By 38 mL n-butanols, the 3 mol/L mL of glucose solution 25,7.3 g PEG 20000s, 2.5 mL dodecyls
Trimethylammonium bromide and 1.1 g stabilizers SY-5 are added in 100 mL twoport round-bottomed flasks；
Flask is placed in precise temperature control electric heating bag, in flask center, interface installs spherical condensation tube, is situated between by cooling of running water
Matter, thermometric thermoelectricity corner is installed in another interface of flask.By adjust electric heating bag heating-up temperature using control in flask solution temperature as
60 DEG C, the min of time 50 is maintained the reflux in this temperature, room temperature is subsequently cooled to, it is standby.
Step 2：Hydrothermal Synthesiss macropore template
The template presoma of preparation is moved into volume in the 100 mL cup-like liner being made up of polytetrafluoroethylmaterial material, to cover
Lid, is placed in stainless steel autoclave；
Autoclave is put in constant temperature electric heating drying box, constant temperature electric heating drying box temperature is risen into 180 ~ 200 DEG C, insulation
36 h.In the process, pressure no more than 3MPa in autoclave is controlled by regulating thermostatic electrically heated drying cabinet temperature；
After device is cooled to room temperature, product is transferred in 200 mL beakers, with 45 MHz frequencies in ultrasonic cleaner
Ultrasonically treated 20 minutes；
By gained solidliquid mixture by cloth funnel suction filtration, after distillation water washing 3 times, then with absolute ethyl alcohol cyclic washing 3
It is secondary, obtain solid filter cake；
Filter cake is placed in constant temperature electric heating drying box, 6 h are dried at 90 DEG C, are then clayed into power in agate mortar, it is standby
With.
Step 3：It is prepared by metatitanic acid cerium precursor
6 mL metatitanic acid isopropyls alcohol esters, 35 mL absolute ethyl alcohols, 13 mL acetone and 1.2 g are separately added into 100 mL beakers to lead
To agent AP-3,20 min are stirred on magnetic stirring apparatus, A liquid is used as；
30 mL absolute ethyl alcohols, 3.6 g Surfactant OPs -3,500 mg macropores templates, 60 mL are added in 200 mL beakers
Distilled water and 2.1 g cerous nitrates, 20 min are stirred on magnetic stirring apparatus, B liquid is used as；
A drops are added in B liquid during magnetic agitation and continue to stir 30 min, by mixed liquor in ultrasonic cleaner
It is standby with ultrasonically treated 1 h of 45 MHz frequencies.
Step 4：Hydrothermal Synthesiss Cerium titanate
Metatitanic acid cerium precursor is moved into volume in the 200 mL cup-like liner being made up of polytetrafluoroethylmaterial material, to close the lid
Son, is placed in stainless steel autoclave；
Autoclave is put in constant temperature electric heating drying box, constant temperature electric heating drying box temperature is risen into 220 ~ 240 DEG C, insulation
72 h.In the process, pressure no more than 3MPa in autoclave is controlled by regulating thermostatic electrically heated drying cabinet temperature；
After device is cooled to room temperature, product is transferred in 200 mL beakers, with 45 MHz frequencies in ultrasonic cleaner
Ultrasonically treated 20 minutes；
By gained solidliquid mixture by cloth funnel suction filtration, after distillation water washing 3 times, then with absolute ethyl alcohol cyclic washing 3
It is secondary, obtain solid filter cake；
Filter cake is placed in constant temperature electric heating drying box, 6 h are dried at 120 DEG C, it is standby.
Step 5：Heat treatment
Filter cake is put into porcelain crucible and is placed in program control cabinet-type electric furnace, furnace temperature is risen to 10 DEG C/min heating rates
1300 DEG C, in this temperature calcination 5 h.Taken out after electric furnace is cooled to room temperature, ground in porcelain mortar and the hollow metatitanic acid of macropore is made
Cerium microballoon.
The rotating speed for the magnetic stirring apparatus being related in the present embodiment is 200 r/min.
Embodiment 4
A kind of preparation method of the hollow Cerium titanate microballoon of macropore, including following processing steps：
Step 1：Prepare template presoma
By 30 mL n-butanols, the 3 mol/L mL of glucose solution 19,5.6 g PEG 20000s, 1.5 mL dodecyls
Trimethylammonium bromide and 0.5 g stabilizers SY-5 are added in 100 mL twoport round-bottomed flasks；
Flask is placed in precise temperature control electric heating bag, in flask center, interface installs spherical condensation tube, is situated between by cooling of running water
Matter, thermometric thermoelectricity corner is installed in another interface of flask；By adjust electric heating bag heating-up temperature using control in flask solution temperature as
60 DEG C, the min of time 50 is maintained the reflux in this temperature, room temperature is subsequently cooled to, it is standby.
Step 2：Hydrothermal Synthesiss macropore template
The template presoma of preparation is moved into volume in the 100 mL cup-like liner being made up of polytetrafluoroethylmaterial material, to cover
Lid, is placed in stainless steel autoclave；
Autoclave is put in constant temperature electric heating drying box, constant temperature electric heating drying box temperature is risen into 180 ~ 200 DEG C, insulation
36 h.In the process, pressure no more than 3MPa in autoclave is controlled by regulating thermostatic electrically heated drying cabinet temperature；
After device is cooled to room temperature, product is transferred in 200 mL beakers, with 45 MHz frequencies in ultrasonic cleaner
Ultrasonically treated 20 minutes；
By gained solidliquid mixture by cloth funnel suction filtration, after distillation water washing 3 times, then with absolute ethyl alcohol cyclic washing 3
It is secondary, obtain solid filter cake；
Filter cake is placed in constant temperature electric heating drying box, 6 h are dried at 90 DEG C, are then clayed into power in agate mortar, it is standby
With.
Step 3：It is prepared by metatitanic acid cerium precursor
5.2 mL metatitanic acid isopropyls alcohol esters, 30 mL absolute ethyl alcohols, 12 mL acetone and 1.25 are separately added into 100 mL beakers
G directed agents AP-3, stir 20 min on magnetic stirring apparatus, are used as A liquid；
30 mL absolute ethyl alcohols, 3.6 g Surfactant OPs -3,500 mg macropores templates, 50 mL are added in 200 mL beakers
Distilled water and 1.5 g cerous nitrates, 20 min are stirred on magnetic stirring apparatus, B liquid is used as；
A drops are added in B liquid during magnetic agitation and continue to stir 30 min, by mixed liquor in ultrasonic cleaner
It is standby with ultrasonically treated 1 h of 45 MHz frequencies.
Step 4：Hydrothermal Synthesiss Cerium titanate
Metatitanic acid cerium precursor is moved into volume in the 200 mL cup-like liner being made up of polytetrafluoroethylmaterial material, to close the lid
Son, is placed in stainless steel autoclave；
Autoclave is put in constant temperature electric heating drying box, constant temperature electric heating drying box temperature is risen into 220 ~ 240 DEG C, insulation
72 h.In the process, pressure no more than 3MPa in autoclave is controlled by regulating thermostatic electrically heated drying cabinet temperature；
After device is cooled to room temperature, product is transferred in 200 mL beakers, with 45 MHz frequencies in ultrasonic cleaner
Ultrasonically treated 20 minutes；
By gained solidliquid mixture by cloth funnel suction filtration, after distillation water washing 3 times, then with absolute ethyl alcohol cyclic washing 3
It is secondary, obtain solid filter cake；
Filter cake is placed in constant temperature electric heating drying box, 6 h are dried at 120 DEG C, it is standby.
Step 5：Heat treatment
Filter cake is put into porcelain crucible and is placed in program control cabinet-type electric furnace, furnace temperature is risen to 10 DEG C/min heating rates
1200 DEG C, in this temperature calcination 6 h.Taken out after electric furnace is cooled to room temperature, ground in porcelain mortar and the hollow metatitanic acid of macropore is made
Cerium microballoon.
The rotating speed for the magnetic stirring apparatus being related in the present embodiment is 200 r/min.
Embodiment 5
A kind of preparation method of the hollow Cerium titanate microballoon of macropore, including following processing steps：
Step 1：Prepare template presoma
By 40 mL n-butanols, the 3 mol/L mL of glucose solution 18,7.5 g PEG 20000s, 2.7mL dodecyls three
Methyl bromide ammonium and 1.2 g stabilizers SY-5 are added in 100 mL twoport round-bottomed flasks；
Flask is placed in precise temperature control electric heating bag, in flask center, interface installs spherical condensation tube, is situated between by cooling of running water
Matter, thermometric thermoelectricity corner is installed in another interface of flask；By adjust electric heating bag heating-up temperature using control in flask solution temperature as
60 DEG C, the min of time 50 is maintained the reflux in this temperature, room temperature is subsequently cooled to, it is standby.
Step 2：Hydrothermal Synthesiss macropore template
The template presoma of preparation is moved into volume in the 100 mL cup-like liner being made up of polytetrafluoroethylmaterial material, to cover
Lid, is placed in stainless steel autoclave；
Autoclave is put in constant temperature electric heating drying box, constant temperature electric heating drying box temperature is risen into 180 ~ 200 DEG C, insulation
36 h.In the process, pressure no more than 3MPa in autoclave is controlled by regulating thermostatic electrically heated drying cabinet temperature；
After device is cooled to room temperature, product is transferred in 200 mL beakers, with 45 MHz frequencies in ultrasonic cleaner
Ultrasonically treated 20 minutes；
By gained solidliquid mixture by cloth funnel suction filtration, after distillation water washing 3 times, then with absolute ethyl alcohol cyclic washing 3
It is secondary, obtain solid filter cake；
Filter cake is placed in constant temperature electric heating drying box, 6 h are dried at 90 DEG C, are then clayed into power in agate mortar, it is standby
With.
Step 3：It is prepared by metatitanic acid cerium precursor
6.3 mL metatitanic acid isopropyls alcohol esters, 35 mL absolute ethyl alcohols, 14 mL acetone and 1.3g are separately added into 100 mL beakers
Directed agents AP-3, stirs 20 min on magnetic stirring apparatus, is used as A liquid；
30 mL absolute ethyl alcohols, 3.6 g Surfactant OPs -3,500 mg macropores templates, 60 mL are added in 200 mL beakers
Distilled water and 2.1 g cerous nitrates, 20 min are stirred on magnetic stirring apparatus, B liquid is used as；
A drops are added in B liquid during magnetic agitation and continue to stir 30 min, by mixed liquor in ultrasonic cleaner
It is standby with ultrasonically treated 1 h of 45 MHz frequencies.
Step 4：Hydrothermal Synthesiss Cerium titanate
Metatitanic acid cerium precursor is moved into volume in the 200 mL cup-like liner being made up of polytetrafluoroethylmaterial material, to close the lid
Son, is placed in stainless steel autoclave；
Autoclave is put in constant temperature electric heating drying box, constant temperature electric heating drying box temperature is risen into 220 ~ 240 DEG C, insulation
72 h.In the process, pressure no more than 3MPa in autoclave is controlled by regulating thermostatic electrically heated drying cabinet temperature；
After device is cooled to room temperature, product is transferred in 200 mL beakers, with 45 MHz frequencies in ultrasonic cleaner
Ultrasonically treated 20 minutes；
By gained solidliquid mixture by cloth funnel suction filtration, after distillation water washing 3 times, then with absolute ethyl alcohol cyclic washing 3
It is secondary, obtain solid filter cake；
Filter cake is placed in constant temperature electric heating drying box, 6 h are dried at 120 DEG C, it is standby.
Step 5：Heat treatment
Filter cake is put into porcelain crucible and is placed in program control cabinet-type electric furnace, furnace temperature is risen to 10 DEG C/min heating rates
1350 DEG C, in this temperature calcination 3 h.Taken out after electric furnace is cooled to room temperature, ground in porcelain mortar and the hollow metatitanic acid of macropore is made
Cerium microballoon.
The rotating speed for the magnetic stirring apparatus being related in the present embodiment is 200 r/min.
Claims (4)
1. a kind of preparation method of the hollow Cerium titanate microballoon of macropore, it is characterised in that including following processing steps：
Step 1：Prepare template presoma；
Step 1.1：By 30 ~ 40 mL n-butanols, the 3 mol/L mL of glucose solution 18 ~ 25,5.6 ~ 7.5 g polyethylene glycol
20000th, 1.5 ~ 2.7 mL DTABs and 0.5 ~ 1.2 g stabilizers SY-5 add 100 mL twoports round bottoms and burnt
In bottle；
Step 1.2：Flask is placed in precise temperature control electric heating bag, in flask center, interface installs spherical condensation tube, with running water
For cooling medium, thermometric thermoelectricity corner is installed in another interface of flask；It is molten in flask to control by adjusting electric heating bag heating-up temperature
Liquid temperature degree is 60 DEG C, and the min of time 50 is maintained the reflux in this temperature, is subsequently cooled to room temperature, prepares template presoma, standby；
Step 2：Hydrothermal Synthesiss macropore template；
Step 2.1：It is 100 mL in the cup-shaped that polytetrafluoroethylmaterial material is made that the template presoma of preparation is moved into volume
In lining, close the lid, be placed in stainless steel autoclave；
Step 2.2：Autoclave is put in constant temperature electric heating drying box, constant temperature electric heating drying box temperature is risen to 180 ~ 200
DEG C, it is incubated 36 h；
Step 2.3：After autoclave is cooled to room temperature, product is transferred in 200 mL beakers, in ultrasonic cleaner
In ultrasonically treated 20 minutes；
Step 2.4：By gained solidliquid mixture by cloth funnel suction filtration, after distillation water washing 3 times, then it is anti-with absolute ethyl alcohol
After backwashing is washed 3 times, obtains solid filter cake；
Step 2.5：Filter cake is placed in constant temperature electric heating drying box, 6 h are dried at 90 DEG C, are then worn into agate mortar
Powder, obtains macropore template, standby；
Step 3：It is prepared by metatitanic acid cerium precursor；
Step 3.1：Be separately added into 100 mL beakers 5.2 ~ 6.3 mL metatitanic acid isopropyls alcohol esters, 30 ~ 35 mL absolute ethyl alcohols,
12 ~ 14 mL acetone and 1.2 ~ 1.3 g directed agents AP-3,20 min are stirred on magnetic stirring apparatus, A liquid is used as；
Step 3.2：30 mL absolute ethyl alcohols, 3.6 g Surfactant OPs -3, the big casements of 500 mg are added in 200 mL beakers
Plate, 50 ~ 60 mL distilled water and 1.5 ~ 2.1 g cerous nitrates, 20 min are stirred on magnetic stirring apparatus, B liquid is used as；
Step 3.3：A drops are added in B liquid during magnetic agitation and continue to stir 30 min, by mixed liquor in ultrasonic wave
Ultrasonically treated 1 h in washer, obtains metatitanic acid cerium precursor, standby；
Step 4：Hydrothermal Synthesiss Cerium titanate；
Step 4.1：Metatitanic acid cerium precursor is moved into the cup-like liner being made up of polytetrafluoroethylmaterial material that volume is 200 mL,
Close the lid, be placed in stainless steel autoclave；
Step 4.2：Autoclave is put in constant temperature electric heating drying box, the temperature of constant temperature electric heating drying box is risen to 220 ~
240 DEG C, it is incubated 72 h；In the process, pressure is controlled in autoclave by regulating thermostatic electrically heated drying cabinet temperature not
More than 3MPa；
Step 4.3：After autoclave is cooled to room temperature, product is transferred in 200 mL beakers, in ultrasonic cleaner
In ultrasonically treated 20 minutes；
Step 4.4：By gained solidliquid mixture by cloth funnel suction filtration, after distillation water washing 3 times, then it is anti-with absolute ethyl alcohol
After backwashing is washed 3 times, obtains solid filter cake；
Step 4.5：Filter cake is placed in constant temperature electric heating drying box, 6 h are dried at 120 DEG C, it is standby；
Step 5：Heat treatment；
Filter cake is put into porcelain crucible and is placed in program control cabinet-type electric furnace, furnace temperature is risen to 10 DEG C/min heating rates
1200 ~ 1350 DEG C, in this temperature calcination 3 ~ 6 h；Taken out after electric furnace is cooled to room temperature, ground in porcelain mortar and macropore is made
Hollow Cerium titanate microballoon.
2. a kind of preparation method of the hollow Cerium titanate microballoon of macropore according to claim 1, it is characterised in that the magnetic force
The rotating speed of agitator is 200 r/min.
3. a kind of preparation method of the hollow Cerium titanate microballoon of macropore according to claim 1, it is characterised in that the step
In 2.2 insulating process, pressure no more than 3MPa in autoclave is controlled by regulating thermostatic electrically heated drying cabinet temperature.
4. a kind of preparation method of the hollow Cerium titanate microballoon of macropore according to claim 1, it is characterised in that
The ultrasonic cleaner is carried out ultrasonically treated with 45 MHz frequencies.
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| CN108033483A (en) * | 2017-12-19 | 2018-05-15 | 沈阳理工大学 | It is a kind of can floating type metatitanic acid praseodymium material preparation method |
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| CN108246361B (en) * | 2018-01-08 | 2020-10-30 | 沈阳理工大学 | Method for preparing molecular sieve type titanium cerium oxide photocatalytic material |
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| JPS5659672A (en) * | 1979-10-16 | 1981-05-23 | Matsushita Electric Ind Co Ltd | Piezoelectric ceramic material |
| CN102502798A (en) * | 2011-11-09 | 2012-06-20 | 南京航空航天大学 | Preparation method for monodisperse barium titanate nanopowder |
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| US4313925A (en) * | 1980-04-24 | 1982-02-02 | The United States Of America As Represented By The United States Department Of Energy | Thermochemical cyclic system for decomposing H2 O and/or CO2 by means of cerium-titanium-sodium-oxygen compounds |
| CN1476929A (en) * | 2003-07-08 | 2004-02-25 | 浙江大学 | Denitration catalyst using CeTi2Ob as carrier and its preparation method |
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| JPS5659672A (en) * | 1979-10-16 | 1981-05-23 | Matsushita Electric Ind Co Ltd | Piezoelectric ceramic material |
| CN102502798A (en) * | 2011-11-09 | 2012-06-20 | 南京航空航天大学 | Preparation method for monodisperse barium titanate nanopowder |
| CN103447022A (en) * | 2013-09-09 | 2013-12-18 | 桂林理工大学 | Visible-light-responsive photocatalyst Ca6Ce2Ti9O28 and preparation method thereof |
| CN103482694A (en) * | 2013-09-29 | 2014-01-01 | 安徽工业大学 | Cerium titanate nanorod and preparation method thereof |
| CN106115779A (en) * | 2016-07-07 | 2016-11-16 | 西安交通大学苏州研究院 | A kind of hollow nano-TiO2the preparation method of bag carbon Yolk shell structure |
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| CN108033483A (en) * | 2017-12-19 | 2018-05-15 | 沈阳理工大学 | It is a kind of can floating type metatitanic acid praseodymium material preparation method |
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